CN105579517A - Highly filled soft polyolefin composition for roofing membrane - Google Patents
Highly filled soft polyolefin composition for roofing membrane Download PDFInfo
- Publication number
- CN105579517A CN105579517A CN201480052951.1A CN201480052951A CN105579517A CN 105579517 A CN105579517 A CN 105579517A CN 201480052951 A CN201480052951 A CN 201480052951A CN 105579517 A CN105579517 A CN 105579517A
- Authority
- CN
- China
- Prior art keywords
- weight
- component
- polyolefin compositions
- less
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
- E04B1/94—Protection against other undesired influences or dangers against fire
- E04B1/941—Building elements specially adapted therefor
- E04B1/942—Building elements specially adapted therefor slab-shaped
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Physics & Mathematics (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Highly filled polyolefin compositions with improved balance of properties particularly for applications where puncture and tear resistance is requested comprising a flexible heterophasic polyolefin composition (I), consisting of a crystalline polymer fraction (A) consisting of a copolymer of propylene with ethylene having a fraction insoluble in xylene at 25DEG C of at least 90% by weight, and an elastomeric fraction (B) consisting of a copolymer or blend of copolymers of ethylene with propylene; said copolymer or blend containing units derived from ethylene in a quantity lower than 40% by weight. The fraction soluble in xylene at 25 DEG C of said polyolefin composition having IVgpc lower than 2.5 dl/g, and a broad molecular weight distribution Mw/Mn (GPC) equal to or higher than 4, Mz/Mw (GPC) equal to or higher than 2.5.The filled polyolefin composition is further comprising of an inorganic filler (II) and a butene-1 copolymer having: flexural modulus (ISO 178) lower than 60 MPa, Shore A (ISO 868) lower than 90 and Tg (DMTA) lower than -20 DEG C.
Description
Technical field
The present invention relates to a kind of soft polyolefin compositions of filling, it is for highly-filled article, sheet material or for the film of roofing and geomembrane, be particularly suitable for the inflaming retarding membrane of the synthesis of the roofing for roofing coverture, be combined with better processibility, the pliability of improvement and good machinery and welding characteristic.Composition of the present invention is also suitable for use in interior packing layer or the lining of industrial cable or cable sheath.
Background technology
Due to the typical valuable characteristic of polyolefine, such as unreactiveness, mechanical characteristics and non-toxic, keep the polyolefin compositions of good thermoplastic behavior to be used to multiple Application Areas so have elastic properties simultaneously.Further, utilize and be used for the constructed of thermoplastic polymer, they should be changed into finished product.Specifically, flexible polymeric materials is widely used in medical field, and for packaging, Extrusion Coating and electric wire and cable coverture.In such applications, use at present the vinyl chloride-base polymer comprising enough softening agent, this softening agent is necessary for the flexible characteristic given with described polymkeric substance needed for them.But the doubtful toxicity of the softening agent that described polymkeric substance comprises because of them is also such as, because when burning, the hypertoxic by product of dioxin can be distributed in air and constantly be scolded by they.Therefore, utilize except required flexible characteristic and the transparency, having material described in the typical unreactiveness of olefin polymer and avirulent products substitution will be very useful.In this field, by optionally comprising the propylene of a small amount of olefin comonomer, and the sequential co-polymerization of ethylene/propene or ethylene/alpha-olefin copolymer mixture is subsequently maintained the elastomeric polypropylenes composition of good thermoplastic behavior.Catalyzer based on the halogenated titanium compound of load on magnesium chloride is usually used in this object.
Such as, EP-A-472946 describes flexible elastoplastic polyolefin composition, and it comprises with parts by weight: A) isotactic propylene homopolymer of 10-50 part or multipolymer; B) ethylene copolymer of 5-20 part, it is at room temperature insoluble in dimethylbenzene; And C) ethylene/propene copolymer of 40-80 part, its comprise be less than by weight 40% ethene and at room temperature dissolve in dimethylbenzene; The limiting viscosity of described multipolymer is preferably 1.7 to 3dl/g.If modulus in flexure is lower than 150MPa value, Shore D hardness 20 to 35, and about Xiao A hardness 90 confirm such, described composition flexible relative also has good elasticity characteristic, relevant to good tension set value (be 20-50% under 75% elongation, and be about 33-40% under 100% elongation); But these values are not entirely satisfactory for many application.Such as the mineral filler of aluminium and magnesium oxyhydroxide or calcium carbonate in polyolefin compositions because multiple reason often uses with high density level, such as, such as, to give self-extinguishing characteristic or improve and apply relevant physical property, flexible touch and impressionability.When particularly using in functional background when fire retardant, the main drawback of these mineral fillers needs very high load.Depend on the grade of required flame retardant resistance, nearly the filler of 65-70% is necessary to reach abundant validity in polyolefine by weight: for flame retardant resistance, also it is enough in some applications for the filler of the relatively low amount of about 40-60% by weight.Usually, this has the negative impact of height to the processing of polymkeric substance, be difficult to add and disperse this high-caliber filler, and to the physical-mechanical properties of compound, there is the negative impact of height, namely lower elongation at break, lower tensile strength and higher fragility.
EP1043733 describes the self extinguishing cable of the coating had based on the polymer materials comprising flame retardant resistance mineral filler.This polymer materials comprise have based on the ethene with alpha-olefin copolymer by weight at least 45% the heterophasic copolymer of elastomerics phase, with based on thermoplastic crystalline's phase of propylene.Although these compositions are incorporated to a large amount of flame retardant filler, very high-caliber filler affects the physical-mechanical properties of polymer materials negatively, particularly causes low elongation value.Therefore, the finished product are no longer suitable for multiple application, such as roofing, film and cable.
Described by more flexible Elastoplastic polyolefin compositions has had in international application WO03/011962, and comprise by weight:
A) crystalline polymer fraction being selected from the multipolymer of alfon and propylene and C4-8 alpha-olefin of 8 to 25%;
B) elastomer portion comprising two kinds of different elastomeric copolymers of propylene of 75 to 92%, more particularly: (1) propylene and the ethene of 15 to 32% and/or the first elastomer copolymer of C4-8 alpha-olefin, and (2) propylene and the ethene of maximum more than 32% 45% and/or the second elastomer copolymer of C4-8 alpha-olefin, (1)/(2) weight ratio is in 1: 5 to 5: 1 scope.
The modulus in flexure that these polyolefin compositionss have is lower than 60MPa, and Shore A is less than 90, and the tension set under 100% elongation is less than 35%.Composition described in this file does not comprise the filler of correlative.
In international application W02004/026957, flexible polyolef compositions of hydrocarbons described in WO03/011962 is filled with the mineral filler of 40-80% by weight, it is selected from flame retardant resistance mineral filler and inorganic oxide or salt, and do not lose their physical-mechanical properties, particularly keep soft and flexural modulus values, high elongation at tear and low-tension deformation values.The Xiao A hardness that highly-filled soft polyolefin compositions described in WO2004/026957 preferably has is less than 90, and elongation at break (ASTMD638) is greater than 400%, fracture tensile strength (ASTMD638) is equal to or higher than 4MPa.
In international application WO2012/152803, disclose be applicable to roof membrane there is the pliability of improvement and the polyolefin compositions of ductility at low temperatures, the flexible heterogeneous compositions (I) with wide molecular weight distribution wherein obtained by mixing the heterogeneous compositions with different melt flow index also mixes with elastomeric component and highly-filled fire retardant.
Summary of the invention
Still feel the demand to such compositions of olefines, when it is suitably compounding with mineral filler, demonstrate the balance of properties of improvement, particularly in the flexibility of such as single-layer roof film and ductility and the processing characteristics serious deterioration of other mechanical property such as particularly tensile property and weldability (and without) application.In special needs also there is high resistance puncture required in the film for roofing coverture and tear strength.
Object of the present invention is the polyolefin compositions of filling, the MFR had is 2 to 7g/10min under 230 DEG C/2.16Kg, it comprises the flexible Heterophasic polyolefin composition (I) be made up of crystalline polymer component (A), and this crystalline polymer component (A) is made up of the multipolymer of propylene and ethene; Described multipolymer comprises the unit of the derived from propylene of by weight at least 85%, described crystallographic component to have at 25 DEG C at least 90% component being insoluble to dimethylbenzene by weight, and the elastomeric component (B) be made up of with the multipolymer of propylene or the blend of multipolymer ethene; Described multipolymer or blend comprise the unit of the derived from ethylene of the amount being less than 40% by weight.
The IVgpc that described polyolefin compositions has in the component that 25 DEG C dissolve in dimethylbenzene is lower than 2.5dl/g, and wide molecular weight distribution Mz/Mw (GPC) is equal to or greater than 4, Mz/Mw (GPC) and is equal to or greater than 2.5.
The polyolefin compositions of filling comprises mineral filler (II) further, and it is selected from flame-retardant inorganic filler and inorganic oxide or salt; And
The polyolefin compositions of this filling comprises 1-Butylene copolymer further, and it has: modulus in flexure (ISO178) is less than 60MPa, Shore A (ISO868) is less than 90, Tg (DMTA) lower than-20 DEG C.
Wherein summation a), b) and c) is 100%.
Detailed Description Of The Invention
The polyolefin compositions of filling of the present invention, the MFR had is 2 to 7g/10min under 230 DEG C/2.16Kg, and it comprises:
A) by weight 35% to 65% flexible Heterophasic polyolefin composition (I), it comprises following component (wherein the summation of A and B component is 100%):
A) be greater than 40% to 50% by weight, preferably by weight 41% to 55%, more preferably by weight 45% to 50% crystalline polymer component, it is made up of the multipolymer of propylene and ethene; Described multipolymer comprises the unit of the derived from propylene of by weight at least 85%, described crystallographic component to have at 25 DEG C the component being insoluble to dimethylbenzene of by weight at least 90%, and the limiting viscosity preferably with dimethylbenzene indissolvable component is 1.2 to 1.9dl/g and the MFR (230 DEG C/2.16Kg) that has is 50 to 80.
B) by weight 45% to being less than 60%, preferably by weight 45% to 59%, more preferably by weight 50% to 55% elastomeric component, it is made up of ethene and the multipolymer of propylene or the blend of multipolymer; Described multipolymer or blend comprise the unit of the derived from ethylene of the amount being less than 40% by weight, preferably by weight 20% to 30% the unit of derived from ethylene, described elastomeric component preferably has the solubleness in the dimethylbenzene (XS) of at room temperature (25 DEG C) being greater than 50% by weight, and the limiting viscosity preferably had is equal to or less than the soluble constituent (XSIV) of 2.3dl/g.
Described polyolefin compositions is dissolved in the IVgpc that the component in dimethylbenzene has and is less than 2.5dl/g, preferably 1.5-2.2dl/g at 25 DEG C; Wide molecular weight distribution Mw/Mn (GPC) is equal to or greater than 4, preferably 6 to 10, Mz/Mw (GPC) and is equal to or greater than 2.5; Even more preferably the MFR of composition A+B is 3-8g/10min under 230 DEG C/2.16Kg, preferably 4-7, even more preferably 5-6g/10min.
B) by weight 30% to 80%, the mineral filler (II) of preferably 30%-55% by weight, it is selected from flame-retardant inorganic filler and inorganic oxide or salt; With
C) 1-Butylene copolymer of 2%-25%, by weight preferably 5%-15% by weight, it has: modulus in flexure (ISO178) is less than 60MPa, is preferably less than 20MPa, Shore A (ISO868) is less than 90, is preferably less than 80, and Tg (DMTA) is lower than-20 DEG C.The tensile deformation even more preferably set at 100% elongation (ISO2285) is less than 45%, is preferably less than 35%.
Wherein summation a), b) and c) is 100%.
The Shore D that highly-filled polyolefin compositions of the present invention demonstrates lower than 50, be preferably lower than 45; Elongation at break (ISO527-3 is technically equal to ASTMD638 standard) is greater than 250%, and be preferably more than 500%, fracture tensile strength (ISO527-3) is equal to or greater than 10, is preferably greater than 15MPa.Obtain the balance of the improvement of flexible, mobility and puncture resistance and tear strength, also keep good weldability simultaneously.
The composition of filling of the present invention is particularly suitable for roofing application, especially single-layer roof coverture, wherein not only material flexibility, elasticity and ductility, and the tear strength of material and puncture resistance install and the building site of using state operate in very important; Apply traction end to gained film to scratch where it itches stress.
" elastomerics " as referred to herein for having low-crystallinity or amorphous polymkeric substance, preferably at room temperature (25 DEG C) in dimethylbenzene solubleness for being greater than 50% by weight, being preferably more than 60%.More preferably, the limiting viscosity according to the soluble constituent η (at 135 DEG C in tetraline) of composition of the present invention (I) is equal to or less than 2.3dl/g, is preferably equal to or less than 2.1.
Composition (I) (component above-mentioned wide molecular weight distribution a) preferably adopting in vitro reactor to obtain at room temperature to measure in the component dissolving in dimethylbenzene.
The MFR preferably had according to composition of the present invention (I) is 3 to 8g/10min, preferably 3.5 to 6g/10min under 230 DEG C/2.16Kg.
According to the preferred embodiments of the invention, Heterophasic polyolefin composition (I) (component a) with mean diameter be 250 microns to 7000 microns, flowable be less than 30 seconds and volume density (by what compress) be greater than 0.4g/ml spheroidal particle form obtain.Heterophasic polyolefin composition (I) can be prepared by being polymerized in polymerization stage in succession, carries out under the existence of polymer materials that wherein each polymerization is subsequently formed in back to back polyreaction above.Polymerization stage can carry out under the existence of Z-N and/or metallocene catalyst.According to preferred embodiment, all polymerization stages carry out in the presence of a catalyst, described catalyzer comprises trialkyl aluminium compound, optionally electron donor(ED) and solid catalyst component, the electronic donor compound capable that solid catalyst component comprises the halogenide of Ti or halogen-alcoholate and is carried on Magnesium Chloride Anhydrous, the surface area (being measured by BET) that described ingredient of solid catalyst has is less than 200m
2/ g, porosity (being measured by BET) is higher than 0.2ml/g.The catalyzer with above-mentioned characteristic is known in the patent literature, particularly advantageously at USP4,399,054 and EP-A-45977 in the catalyzer that describes.Other examples can at USP4, and 472, find in 524.In international application EP-A-472946, describe polymerization process in detail, its content is incorporated herein by reference.
Polymerization stage can occur in the liquid phase, in the gas phase or in liquid-gas phase.Preferably, the polymerization of crystalline polymer component (A) with liquid monomer (such as, use propylene liquid as thinner) carry out, the copolymerization stage of the elastocopolymer simultaneously in component (B) is carried out in the gas phase, and the intermediate stage not except the partly degassed of propylene.According to the most preferred embodiment, all polymerization stages in succession carry out in the gas phase.Temperature of reaction in the preparation of the elastocopolymer in the polymerization stage for the preparation of crystalline polymer component (A) and in component (B) can be identical or different, and preferably 40 DEG C to 90 DEG C; More preferably, in the preparation of component (A), range of reaction temperature is 50 DEG C to 80 DEG C, and is 40 DEG C to 80 DEG C for the preparation temperature scope of component (B).If carried out with liquid monomer, the pressure so preparing the polymerization stage of component (A) is the vapour pressure pressure of competition with propylene liquid under used service temperature, and it can by the vapour pressure of the inert diluent of a small amount of for feeding catalyst mixture, by the superpressure of optional monomers and revised by the hydrogen being used as molecular weight regulator.If carried out in the liquid phase, the scope of polymerization pressure is preferably 33bar to 43bar, and if carry out in the gas phase, polymerization pressure is 5bar to 30bar.Residence time about two stages depends on the ratio between required component (A) and (B), and usually can at 15 minutes in 8 hours window.Convenient molecular weight conditioning agent known in the art can be used, such as chain-transfer agent (such as, hydrogen or ZnEt
2).
Alternatively, can to extrude or blended in mixing equipment (such as melt blending) obtains in routine by independent production component and subsequently according to composition of the present invention (I).
The 1-Butylene copolymer with one or more following preferred properties is preferably according to 1-Butylene copolymer of the present invention (amount of component b):
The content of butene-1 derived units is by weight 80% or higher, is preferably by weight 84% or higher;
Flexural modulus of elasticity is preferably 40MPa or less, is even more preferably 30MPa or less; Melt temperature DSC (TmI), lower than 110 DEG C, is preferably equal to or less than 50 DEG C.
1-Butylene copolymer (amount of component b) can be prepared under existing according to the metallocene catalyst of WO2009/000637 (it is incorporated to herein by reference).
Described 1-Butylene copolymer component (amount of component b) is further preferably 1-butylene/ethylene copolymer, and the ethylene content of its copolymerization is by mol 5% to 18.00%, preferably by mol 15.50% to 17%; There is one or more following preferred property:
A) molecular weight distribution mw/mn is less than 3;
B) Xiao A hardness (measuring according to ISO868) is less than 65, is preferably less than 60;
C) tension set (ISO2285) under 100% distortion is less than 30%, is preferably less than 20%;
D) under DSC, do not have the fusing point that can detect, the thermal history of offsetting multipolymer according to the method described in the document is measured;
E) have between 4J/g to 15J/g, the melting enthalpy preferably between 5J/g to 10J/g, measure according to the method described in this document, measure after at room temperature aging 10 days;
F) content of the 1-butylene unit of isotaxy five-tuple (mmmm) form is higher than 90%, preferably higher than 98%
Described 1-Butylene copolymer (amount of component b) can be advantageously by the composition formed as follows further:
I) by weight 80% or higher, preferably by weight 85% to 95%, more preferably by weight 90% to 93% described 1-Butylene copolymer, and
Ii) high to 20% by weight, preferably by weight 5% to 15%, more preferably by weight 7% to 10% crystalline propene polymer; Assuming that the total content of the ethene of copolymerization and propylene is equal to or less than 16% of composition (i)+(ii) by weight.
Crystalline propene polymer (ii) is propylene copolymer preferably, is more preferably propylene trimer, is even more preferably multipolymer or its blend of propylene and ethene and C4-C8 alpha-olefin.The overall processability of 1-Butylene copolymer component (c) advantageously can improve by mixing the high described crystalline propene polymer component (ii) to 20% by weight in line, and other mechanical propertys not deteriorated in fact.Crystalline propene polymer (ii) usually 230 DEG C, melt flow rate (MFR) (MFR) value under 2.16kg is 0.6g/10min to 10g/10min, preferably 2g/10min to 10g/10min, melt temperature DSC is 130 DEG C to 160 DEG C.
The total content of the ethene in crystalline propene polymer (ii) is preferably 1% to 5% by weight, and the total content of C4-C8 alpha-olefin in component (ii) is 2.4% to by weight 12% by weight.
Highly-filled soft polyolefin compositions according to the present invention also comprises mineral filler (II) (components b), and it is selected from flame-retardant inorganic filler and inorganic oxide or salt.
In the application of demand self-extinguishment, preferred component (b) flame-retardant inorganic filler is the oxyhydroxide of metal (particularly Ca, Al or Mg), hydrous oxide, salt or salt hydrate, such as: magnesium hydroxide Mg (OH)
2, aluminium hydroxide Al (OH)
3, hibbsite Al
2o
33H
2o, hydrocarbonate of magnesia, magnesiumcarbonate MgCO
3, hydrated calcium magnesium carbonate, magnesium calcium carbonate or its mixture.Mg (OH)
2, Al (OH)
3, Al
2o
33H
2o and its mixture are particularly preferred.Metal hydroxides, especially magnesium hydroxide and aluminium hydroxide, preferably use size can 0.1 to 100 μm, be preferably 0.5 to 10 μm within the scope of particulate forms.Be precipitated magnesium hydroxide according to the especially preferred a kind of mineral filler of the present invention, it has 1 to 20m
2/ g, preferably 3 to 10m
2the specific surface area of/g, from the median size of 0.5 to 15 μm, preferably 0.6 to 1 μm of scope.And precipitated magnesium hydroxide comprises the impurity of minute quantity usually, it comes from salt, the oxide compound and/or oxyhydroxide etc. of other metals such as Fe, Mn, Ca, Si, V.The amount of this type of impurity and character depend on the source of starting material.The grade of purity is generally 90 to 99% by weight.Filler can advantageously use with the form of enwrapped granule.The lapping of preferential employing contains from the saturated of 8 to 24 carbon atoms or unsaturated fatty acids, and metal-salt, such as oleic acid, palmitinic acid, stearic acid, Unimac 5680, lauric acid and stearic acid or magnesium oleate or zinc.Inorganic oxide or salt are preferably selected from CaO, TiO
2, Sb
2o
3, ZnO, Fe
2o
3, CaCO
3, BaSO
4and composition thereof.
Highly-filled soft polyolefin compositions according to the present invention is by making polymeric constituent, filler and optionally the mixing of other additive is obtained according to ordinary method known in the art.Such as, these components can there is tangential rotors (as Banbury mixing roll) or have IPN rotor Banbury mixer or alternatively at continuous mixer (as Buss mixing roll) or mix in the same way or in the double-screw mixer of reverse rotation.
Polymeric component of the present invention can mix a large amount of fillers, remains physics and the mechanical characteristics of the composition of unfilled and flexibility difference simultaneously.More particularly, highly-filled polyolefin compositions of the present invention preferably has the modulus in flexure (ISO178 puts on compression molded sample 1mm thick) from 300 to 800MPa, preferably higher than 500MPa.Therefore, according to the component (c) that interpolation of the present invention and component (a) are combined, obtain the Value balance of performance.Even if obtain the raising in puncture and anti tear under relatively high rigidity (modulus in flexure).
Filled polyolefin composition of the present invention is suitable for and substitutes as plasticized PVC.In the field of demand self-extinguishment, composition of the present invention can use plasticized PVC to replace, for such as strengthen and non-reinforcing roof membrane, in application for the inner stuffing of industrial cable, cable sheath and sealing tape.
Therefore, the invention further relates to the goods comprising above-mentioned filled polyolefin composition.Specifically and preferably it also relates to the film or sheet material that blowing or salivation be applicable to apply in roofing and geomembrane.
The conventional additives that this area is commonly used can be added into highly-filled soft polyolefin compositions of the present invention.Such as, for increasing the consistency between mineral filler and heterophasic polymer composition, coupling agent can be used; Described coupling agent can be saturated silane compound or containing at least one ethylenically unsaturated group silane compound, epoxide containing an ethylenically unsaturated group, organic titanate, monoprotic acid or the diprotic acid containing at least one ethylenically unsaturated group, or derivatives thereof as acid anhydride or ester.
The monoprotic acid containing at least one ethylenically unsaturated group or the diprotic acid or derivatives thereof that can be used as coupling agent are, such as, toxilic acid, maleic anhydride, fumaric acid, citraconic acid, methylene-succinic acid, vinylformic acid, methacrylic acid etc. and by its derivative acid anhydrides or ester or its mixture.Particularly preferably be maleic anhydride.
Coupling agent can be used as this type of or by means (being such as the described in EPA-530940) graft polymerization preformer of free radical reaction to polyolefine, the multipolymer of such as polyethylene or ethene and alpha-olefin.The amount of By Grafting-coupling Agent relative to 100 weight parts polyolefine usually between 0.05 to 5 weight part, preferably from 0.1 to 2 weight part.With the polyolefine of maleic anhydride graft usually used as commerical prod, the poly thio rubber adhesive 3200 such as produced by Chemtura (Chemtura) or Basel (Basell).
Alternatively, the coupling agent (such as maleic anhydride) of above-mentioned carboxylic acid or epoxy type or can be added into containing the silane (such as vinyltrimethoxy silane) of ethylenically unsaturated group mixture combine with radical initiator and consequently compatibilizing agent is directly grafted on polymer materials.Spendable initiator is organo-peroxide, such as peroxidized t-butyl perbenzoate, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide etc.Such as, at USP4,317, describe this technology in 765.
The amount of adding the coupling agent in described mixture to can according to the amount change of the fire-retardant filler of the character of used coupling agent and interpolation, and relative to highly-filled polyolefin compositions gross weight by weight preferable range from 0.01 to 10%, be more preferably from 0.1 to 5%, and even more excellent be from 1 to 3%.Also can add the conventional additives usually used in olefin polymer, such as processing aid, lubricant, nucleator, extension oily, organic and mineral dye, antioxidant and UV-protective agent.
Usually the processing aid added in polymer materials is, such as, and calcium stearate, Zinic stearas, stearic acid, paraffin, synthetic oil and silicon rubber.The example of suitable antioxidant is the trimethyldihydroquinoline, 4 of polymerization, 4 ' thiobis (3-methyl-6-tert butyl) phenol; Four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and 2,2 '-thiodiethyl two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester].
Other operable fillers are, such as, and glass particle, glass fibre, calcined kaolin and talcum.
Following analytical procedure has been used to measure the character reported in the application.
Embodiment
Provide following embodiment for illustration of the present invention, but be not for limiting object.
Following analytical procedure is used to measure the character reported in specification sheets and embodiment.
melt flow rate (MFR)-do not specify in MFRISO1133 under 230 DEG C of 2.16kg discriminatively.
via MWD and IV that GPD measuresmolecular weight distribution and correlation parameter Mn, Mz and IVgpc value are used by gel permeation chromatography (GPC) method and are equipped with the AllianceGPCV2000 instrument (Waters) of four mixed bed column PLgelOlexisAgilent with 13 μm of granularities to measure at 150 DEG C.Described column dimension is 300 × 7.8mm.Moving phase used is 1,2, the 4-trichlorobenzene (TCB) of vacuum distilling, and flow rate remains on 1.0ml/min.By in TCB in 150 DEG C stir under heating sample within about 2 hours, prepare sample solution.Concentration is 1mg/ml.For preventing degraded, add the 2,6 ditertiary butyl p cresol of 0.1g/l.The solution of 308.5 μ L is injected post group.Adopt molecular weight ranges be 580 to 7500000 10 polystyrene standard sample (the EasiCal assembly provided by PolymerLaboratories) obtain working curve.Assuming that the K value of Mark-Houwink relational expression is:
For polystyrene standard sample, K=1.21 × 10
-4dL/g and α=0.706;
For copolymerization of propylene matter sample, K=2.46 × 10
-4dL/g and α=0.725.
Cubic polynomial matching is used for loading test data and obtains working curve.Data acquisition and process be by together with use Empower1.0 and the GPCV option of Waters to complete.
For butene-1 polymer, when using for PSMark-Houwink index α=0.706 with for PB α=0.725, Mark-Houwink relational expression is used for determining molecular weight distribution and molecular-weight average of being correlated with: be respectively KPS=1.21 × 10 for PS and PB, K value
-4dL/g and KPB=1.78 × 10
-4dL/g.
For ethylene/butylene copolymers, about involved data evaluation, assuming that be constant for each sample at the gamut composition of molecular weight and adopt following listed linear combination to calculate the K value of Mark-Houwink relational expression:
K
EB＝x
EK
PE+x
PK
PB
Wherein K
eBthe constant of multipolymer, K
pE(4.06 × 10
-4, dL/g) and K
pB(1.78 × 10
-4dL/g) be the constant of polyethylene and polybutene, x
eand x
bethene and butylene % content by weight.Mark-Houwink index α=0.725 independently on their composition for all butylene/ethylene copolymers.
For butylene/propylene copolymer, because PP and PB has very similar K, do not apply correction, and adopt the integrated multipolymer of K and α value of PB.
tensile property: tensile modulus (Young), yield strength and elongation, breaking tenacity and elongation are measured according to ISO527-1-3.
modulus in tension(MET-DMTA) modulus in tension (storage modulus) to be analyzed via DMA at 23 DEG C and is measured on the thick holoplast of 1mm according to ISO6721-4.
flexural modulus of elasticity(MEF) ISO178
By be used for tensile modulus and modulus in flexure test
samplefrom under holoplast cutting, this holoplast to be pressed and via autoclave in 2kbar at room temperature ageing 10 ' at 200 DEG C.Sample thickness 4mm.Surrender and fracture tensile strength and elongation are from the 30mm with the thick flat die of 1mm, 25L/D Brabender (Brabender) single screw extrusion machine is extruded and machine direction cutting and test 1mm sheet material and the sample that obtains is measured according to ISO527-3 (project 5A, 500mm/min).(MD); Also measure modulus in tension on these samples.
shore (Sh.A) and Shore D (Sh.D) hardnessmeasured by upper at holoplast (4mm thickness) according to ISO868.
tear strengthaccording to ASTMD1004.
puncture resistanceaccording to ASTMD4833.
co-monomer content(% by weight) IR. spectrum
limiting viscositymeasured in tetraline at 135 DEG C.
xylene soluble and soluble part(% is by weight): measure by following:
By the polymer composition of 2.5g and 250cm
3o-Xylol be incorporated in the glass flask being equipped with refrigerator and magnetic stirring apparatus.Temperature was brought up in 30 minutes the boiling point of solvent.The clear solution so obtained is kept backflow, and stirs 30 minutes further.Then closed flask was under agitation cooled to 100 DEG C at 10 to 15 minutes in atmosphere, then keeps in water bath with thermostatic control keeping 30 minutes at 25 DEG C equally for 30 minutes.Fast grade filter paper filters the solid so formed.By 100cm
3filtrate be poured in the aluminum container of weighing in advance, it heats on hot plate under nitrogen gas stream condition, to pass through evaporation of solvent.Then container is remained under vacuum in 80 DEG C of vacuum drying ovens until obtain constant weight.Then at room temperature (25 DEG C) calculate the weight percent dissolving in the polymkeric substance of dimethylbenzene (XS).
On PerkinElmerDSC-7 instrument, butene-1 polymer is measured by dsc (D.S.C.)
thermal characteristics (melt temperature and enthalpy).The melt temperature of 1-butylene homopolymer and multipolymer is measured according to following methods:
-TmII (measured by second time heat-processed): be encapsulated into aluminium dish from being polymerized the sample (5-10mg) of weighing obtained, and heat at 200 DEG C with the sweep velocity corresponding to 20 DEG C/min.At sample being remained on 200 DEG C 5 minutes, melt to make all crystals the thermal history eliminating sample thus completely.Then, after being cooled to-20 DEG C corresponding to the sweep velocity of 10 DEG C/min, peak temperature is regarded as Tc (Tc).After leaving standstill 5 minutes at-20 DEG C, sample was heated for the second time with the sweep velocity corresponding to 10 DEG C/min at 200 DEG C.In this second time heat-processed, peak temperature is regarded as the temperature of fusion of poly 1-butene (PB) crystallized form II (TMII) and area is regarded as total fusion enthalpy (Δ HfII) when it is present.
The fusion enthalpy of-TmI crystallized form after I10 days and temperature of fusion are measured by following by using dsc (D.S.C.) on PerkinElmerDSC-7 equipment: be encapsulated into aluminium dish from being polymerized the sample (5-10mg) of weighing obtained, and heat at 200 DEG C with the sweep velocity corresponding to 20 DEG C/min.At sample being remained on 200 DEG C 5 minutes, melt completely to make all crystals.Then, sample is at room temperature stored 10 days.After 10 days, DSC is carried out to sample, be cooled to-20 DEG C, then it is heated with the sweep velocity corresponding to 10 DEG C/min at 200 DEG C.In this heat-processed, in thermogram, be regarded as temperature of fusion (TmI) from the first peak temperature of low temperature side, and area be considered as the total fusion enthalpy (Δ Hf) after 10 days.Sometimes, Tml and the TMII thermal spike of winding can prove by this method at least partly.(Δ Hf) is the total enthalpy mensuration as the overall peak of winding at least partly.
When case of propylene crystallinity come from crystalling propylene polymkeric substance exist to the addition of butene-1 polymer (components b) time, another temperature of fusion peak (PP) can detect at a higher temperature.
dMTA analyzes
The shaping sample of 76mmx13mmx1mm is fixed on DMTA machine to be tested for tensile stress.The frequency of pulling force and the dependence of sample are fixed on 1Hz.DMTA changes the elastic response of sample starting form-100 DEG C to 130 DEG C.By this way, the curve of elastic response to temperature can be drawn.Young's modulus for viscoelastic material is defined as E=E '+iE ".DMTA can by their resonance and curve E ' to temperature and E '/E "=tan (δ) splits two component E ' and E to temperature ".
Glass transition temperature Tg is assumed that it is at curve E '/E "=tan (δ) is to the temperature at the maximum value place of temperature.
Following material uses in working Examples
HPOl: Heterophasic polyolefin composition, there is MFR6g/10min, MEF220MPa, Shore D hardness (Sh.D) 41, the total Xylene-Soluble Fraction had is by weight 50.5%, the limiting viscosity 2.15dl/g of solvend (XSIV), Mw/Mn8.4, Mz/Mw3.5, IVgpc1.71dl/g.HPO1 comprises with lower part/component:
By weight 46.5% propylene (A) crystalline copolymer with by weight 3.5% the unit of derived from ethylene, its MFR had is 75g/10min, soluble part by weight 6% in dimethylbenzene at 25 DEG C, and
The propylene of 53.5% and the elastomer portion of ethene (B) by weight, it has the unit of the derived from ethylene of by weight 25%, and Xylene-Soluble Fraction at 89% 25 DEG C by weight.
HPO2:(contrasts properties-correcting agent, soft heterophasic propylene composition) Heterophasic polyolefin composition, comprise the crystalline copolymer of the propylene of by weight 15%, have by weight 3.3% and the propylene of by weight 85% and the elastomer portion of ethene, as prepared in the embodiment 3 of international application no WO03/011962.Elastoplastic polymer superoxide (100ppmLuperox101) limiting viscosity of part solvend in viscosity breaking to the final melt index MFR (230 DEG C/2.16kg) of 2.8g/10min and the dimethylbenzene of 2dl/g in twin screw Berstoff forcing machine.Before viscosity breaking, the polymkeric substance of embodiment 3 demonstrates the limiting viscosity of part solvend in the dimethylbenzene of MFR and 4.57dl/g of 0.07g/10min.HPO2 modulus in flexure (ISO178) is 35MPa, and Shore A (ISO868) is that 75, Tg (DMTA) is-23 DEG C.
PB1 is the butene-1/ethylene copolymer prepared according to the method described in WO2009/000637 embodiment 4.
PB2 is obtained from PB1 by online compounding crystallization terpolymer (ii), wherein crystallization terpolymer (ii) with 7% of the weight relative to copolymer compositions (A)=(i)+(ii)=PB1+ (ii) amount add.PB2 (amount of component b) has the ethylene copolymer content of by weight 8.5%, and melting index MFR (190 DEG C/2.16kg) is 1dl/g.Modulus in flexure MEF (ISO178) is 12MPa, and to be 64.5, Tg (DMTA) be-27 DEG C and be 18% in the permanentset of 100% elongation place (ISO2285) to Shore A (ISO868).Be the non-detectable and TmI40.3 DEG C of TmII for polybutene component DSC temperature.
MDH-Mg (OH)
2: the Kisuma5A-C of KyowaChemicalIndustry, the precipitated magnesium hydroxide being coated with lipid acid for the mean particle size with 0.94 micron, the compatible polyolefin of purity 97.65%.
Table 1 and table 2 report each group component (by weight %) according to the composition of the present invention and comparative example and character.
Table 1
Table 2
Observe, relative to other soft properties-correcting agent (HPO2) obtainable in prior art, select soft properties-correcting agent c) combine the tear strength of composition and the sizable improvement of puncture resistance that a) provide filling according to specific components of the present invention, even if be also like this under modification comparatively in a small amount.
Claims (9)
1. a polyolefin compositions of filling, the MFR had is under 230 DEG C/2.16Kg 2 grams/10 minutes to 7 grams/10 minutes, and it comprises:
A) by weight 35% to 65% flexible Heterophasic polyolefin composition (I), comprise following component:
A) crystalline polymer component be made up of the multipolymer of propylene and ethene of 40% to 55% is greater than by weight; Described multipolymer comprises the unit of the derived from propylene of at least by weight 85%, and described crystallographic component to have at 25 DEG C the component being insoluble to dimethylbenzene of at least by weight 90%;
B) by weight 45% to the elastomeric component be made up of with the multipolymer of propylene or the blend of multipolymer ethene being less than 60%; Described multipolymer or blend comprise the unit of derived from ethylene with the amount being less than by weight 40%; And
The IVgpc that the component dissolving in dimethylbenzene at 25 DEG C of described polyolefin compositions (I) has is less than 2.5dl/g, and wide molecular weight distribution Mw/Mn (GPC) is equal to or higher than 4, Mz/Mw (GPC) and is equal to or higher than 2.5;
B) by weight 30% to 80% mineral filler (II), described mineral filler (II) is selected from flame-retardant inorganic filler and inorganic oxide or salt;
C) by weight 2% to 25% 1-Butylene copolymer, the modulus in flexure (ISO178) that described 1-Butylene copolymer has is less than 60MPa, Xiao A hardness (ISO868) be less than 90 and Tg (DMTA) lower than-20 DEG C;
Wherein summation a), b) and c) is 100%.
2. the polyolefin compositions of filling according to claim 1, the solubleness of described elastomeric component B at room temperature in dimethylbenzene of wherein said component (a) is greater than 50% by weight.
3., according to the polyolefin compositions of filling in any one of the preceding claims wherein, the MFR had is from 3 grams/10 minutes to 8 grams/10 minutes under 230 DEG C/2.16Kg.
4., according to the polyolefin compositions of filling in any one of the preceding claims wherein, wherein said mineral filler (II) is the flame-retardant inorganic filler being selected from the oxyhydroxide of metal, hydrous oxide, salt and salt hydrate.
5. according to the polyolefin compositions of filling in any one of the preceding claims wherein, wherein said amount of component b) be 1-Butylene copolymer, have:
The content of-butene-1 derived units is by weight 80% or higher
-melt temperature DSC (TmI) is less than 110 DEG C.
6., according to the polyolefin compositions of filling in any one of the preceding claims wherein, its Shore D hardness had is less than 50, and elongation at break is higher than 250%, and fracture tensile strength is equal to or higher than 10MPa.
7. one kind comprises the goods of polyolefin compositions according to any one of claim 1 to 6.
8. one kind comprises the sheet material for roofing or the film of polyolefin compositions according to any one of claim 1 to 6.
9. one kind comprises the inner stuffing for industrial cable or cable sheath of polyolefin compositions according to any one of claim 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13188697 | 2013-10-15 | ||
| EP13188697.0 | 2013-10-15 | ||
| PCT/EP2014/071020 WO2015055433A1 (en) | 2013-10-15 | 2014-10-01 | Highly filled soft polyolefin composition for roofing membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105579517A true CN105579517A (en) | 2016-05-11 |
| CN105579517B CN105579517B (en) | 2017-11-17 |
Family
ID=49354561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480052951.1A Active CN105579517B (en) | 2013-10-15 | 2014-10-01 | Highly-filled soft polyolefin compositions for roof membrane |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US9932470B2 (en) |
| EP (1) | EP3058028B1 (en) |
| CN (1) | CN105579517B (en) |
| BR (1) | BR112016006965B1 (en) |
| WO (1) | WO2015055433A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113924339A (en) * | 2019-06-24 | 2022-01-11 | Sika技术股份公司 | Thermoplastic polymer composition with improved flexibility |
| CN115516017A (en) * | 2020-05-22 | 2022-12-23 | 巴塞尔聚烯烃意大利有限公司 | Highly filled and flexible polyolefin compositions |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017089125A1 (en) * | 2015-11-24 | 2017-06-01 | Basell Polyolefine Gmbh | Polyolefin compositions and articles manufactured therefrom |
| US10669414B2 (en) * | 2016-03-10 | 2020-06-02 | Exxonmobil Chemical Patents Inc. | Propylene-based elastomers for roofing compositions and methods for preparing the same |
| MX2020000429A (en) * | 2019-01-10 | 2021-01-08 | Building Mat Investment Corp | Liquid applied roofing system with improved water barrier layer. |
| JP7322449B2 (en) * | 2019-03-22 | 2023-08-08 | 凸版印刷株式会社 | Complementary base material for fire-resistant structure and method for manufacturing complementary base material for fire-resistant structure |
| EP3819317A1 (en) * | 2019-11-07 | 2021-05-12 | Sika Technology Ag | Waterproofing membrane with a self-healing layer |
| EP3940003A1 (en) * | 2020-07-16 | 2022-01-19 | Borealis AG | Translucent polyolefin blends achieving excellent impact-stiffness balance and flowability |
| MX2023006890A (en) | 2020-12-11 | 2024-03-22 | Bmic Llc | Liquid applied roofing formulations and methods of using the same to coat at least one steep slope roof substrate. |
| EP4259719A1 (en) | 2020-12-14 | 2023-10-18 | Basell Poliolefine Italia S.r.l. | Ultrasoft polyolefin composition |
| WO2023117512A1 (en) * | 2021-12-23 | 2023-06-29 | Basell Poliolefine Italia S.R.L. | Soft polyolefin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102639623A (en) * | 2009-12-17 | 2012-08-15 | 3M创新有限公司 | Nanocalcite and vinyl ester composites |
| WO2012152803A1 (en) * | 2011-05-11 | 2012-11-15 | Basell Poliolefine Italia S.R.L. | Highly filled soft polyolefin compositions |
| EP2660287A1 (en) * | 2012-05-04 | 2013-11-06 | Basell Poliolefine Italia S.r.l. | Highly filled soft polyolefin compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1264681B1 (en) | 1993-07-07 | 1996-10-04 | Himont Inc | PARTLY CROSS-LINKED POLYOLEFINIC COMPOSITION |
| CN102666709B (en) * | 2009-11-17 | 2015-08-26 | 巴塞尔聚烯烃意大利有限责任公司 | There is the soft polyolefin compositions improving processibility |
-
2014
- 2014-10-01 WO PCT/EP2014/071020 patent/WO2015055433A1/en active Application Filing
- 2014-10-01 CN CN201480052951.1A patent/CN105579517B/en active Active
- 2014-10-01 BR BR112016006965-0A patent/BR112016006965B1/en active IP Right Grant
- 2014-10-01 EP EP14781139.2A patent/EP3058028B1/en active Active
- 2014-10-01 US US15/029,470 patent/US9932470B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102639623A (en) * | 2009-12-17 | 2012-08-15 | 3M创新有限公司 | Nanocalcite and vinyl ester composites |
| WO2012152803A1 (en) * | 2011-05-11 | 2012-11-15 | Basell Poliolefine Italia S.R.L. | Highly filled soft polyolefin compositions |
| EP2660287A1 (en) * | 2012-05-04 | 2013-11-06 | Basell Poliolefine Italia S.r.l. | Highly filled soft polyolefin compositions |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113924339A (en) * | 2019-06-24 | 2022-01-11 | Sika技术股份公司 | Thermoplastic polymer composition with improved flexibility |
| CN113924339B (en) * | 2019-06-24 | 2024-01-26 | Sika技术股份公司 | Thermoplastic polymer composition with improved flexibility |
| CN115516017A (en) * | 2020-05-22 | 2022-12-23 | 巴塞尔聚烯烃意大利有限公司 | Highly filled and flexible polyolefin compositions |
| CN115516017B (en) * | 2020-05-22 | 2023-09-26 | 巴塞尔聚烯烃意大利有限公司 | Highly filled and flexible polyolefin compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160257809A1 (en) | 2016-09-08 |
| US9932470B2 (en) | 2018-04-03 |
| BR112016006965A2 (en) | 2017-08-01 |
| EP3058028A1 (en) | 2016-08-24 |
| EP3058028B1 (en) | 2018-07-04 |
| WO2015055433A1 (en) | 2015-04-23 |
| BR112016006965B1 (en) | 2021-09-21 |
| CN105579517B (en) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105579517A (en) | Highly filled soft polyolefin composition for roofing membrane | |
| US9260597B2 (en) | Highly filled soft polyolefin compositions | |
| US9290648B2 (en) | Soft polyolefin compositions and highly filled compounds thereof | |
| US7125924B2 (en) | Highly filled soft polyolefin compositions | |
| US9434827B2 (en) | Polymer blend comprising propylene-based elastomer and random copolymer polypropylene | |
| KR101004251B1 (en) | Thermoplastic polymer composition, method for producing thermoplastic polymer composition, molded body obtained from thermoplastic polymer composition and electric wire | |
| JP6230629B2 (en) | Blow molding composition | |
| EP1546256B1 (en) | Highly filled soft polyolefin compositions | |
| EP2660287A1 (en) | Highly filled soft polyolefin compositions | |
| MX2015001700A (en) | Polyolefin compositions and articles manufactured therefrom. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |